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Lead is one of the key metals of the all-inorganic lead halide perovskites. This work tailors novel architectures of lead's coordination sphere using a β-diketone (H-hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione) and a glyme (monoglyme, diglyme, triglyme, or tetraglyme) ligand. The coordination chemistry and thermal behaviour of these "Pb(hfa)2·glyme" adducts have been analysed through FT-IR spectroscopy, 1H and 13C NMR analyses, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). Single-crystal X-ray diffraction studies provide evidence of the formation of a monomeric Pb(hfa)2·monoglyme structure. In order to validate the potentiality of these "Pb(hfa)2·glyme" precursors for the fabrication of Pb-based halide perovskites, a facile, one-step and low-temperature solution approach has been applied to prepare CsPbBr3 microcrystals with a process carried out in air under atmospheric pressure. Pure stoichiometric CsPbBr3 powders, obtained using Cs(hfa) and Br2 as cesium and bromide sources, respectively, show excellent stability under atmospheric conditions. Better results are obtained in terms of yield and stability from the diglyme and tetraglyme lead adducts. Field emission scanning electron microscopy (FE-SEM) indicates a good uniform morphology of cubic grains, while the structure and the 1 : 1 : 3 stoichiometry of Cs : Pb : Br are confirmed by X-ray diffraction (XRD) and energy dispersive X-ray analysis (EDX), respectively. Tauc plots derived from absorption spectroscopy point to optical energy band-gaps (Eg) in the 2.21–2.27 eV range, in agreement with literature data. The present research elucidates the potential of these novel "Pb(hfa)2·glyme" adducts as promising lead precursors for CsPbBr3 perovskite synthesis, paving the way for their implementation in various technological applications. [ABSTRACT FROM AUTHOR]

The globally widespread perfluorooctanoic acid (PFOA) is a concerning environmental contaminant, with a possible toxic long-term effects on the environment and human health The development of sensible, rapid, and low-cost detection systems is a current change in modern environmental chemistry. In this context, two triamine-based chemosensors, L1 and L2, containing a fluorescent pyrene unit, and their Zn(II) complexes are proposed as fluorescent probes for the detection of PFOA in aqueous media. Binding studies carried out by means of fluorescence and NMR titrations highlight that protonated forms of the receptors can interact with the carboxylate group of PFOA, thanks to salt bridge formation with the ammonium groups of the aliphatic chain. This interaction induces a decrease in the fluorescence emission of pyrene at neutral and slightly acidic pH values. Similarly, emission quenching has also been observed upon coordination of PFOA by the Zn(II) complexes of the receptors. These results evidence that simple polyamine-based molecular receptors can be employed for the optical recognition of harmful pollutant molecules, such as PFOA, in aqueous media. [ABSTRACT FROM AUTHOR]

Pannexins are an interesting new target in medicinal chemistry, as they are involved in many pathologies such as epilepsy, ischemic stroke, cancer and Parkinson's disease, as well as in neuropathic pain. They are a family of membrane channel proteins consisting of three members, Panx-1, Panx-2 and Panx-3, and are expressed in vertebrates. In the present study, as a continuation of our research in this field, we report the design, synthesis and pharmacological evaluation of new quinoline-based Panx-1 blockers. The most relevant compounds 6f and 6g show an IC50 = 3 and 1.5 µM, respectively, and are selective Panx-1 blockers. Finally, chemical stability, molecular modelling and X-ray crystallography studies have been performed providing useful information for the realization of the project. [ABSTRACT FROM AUTHOR]

In this paper, the use of Metal-Organic Framework (MOF) materials as an option for the energy efficiency enhancement of HVAC systems is investigated. In particular, the possibility of using MOFs as dehumidifying materials to reduce the latent load associated with the moisture content of the airflows is studied. A literature review is proposed, highlighting the benefits of using MOFs instead of other adsorbents (e.g., silica-gel) and discussing the unique features (high water uptake capacity and low regeneration temperatures) that make MOFs a preferential desiccant. The possibility to finely tune these properties is also underlined, reporting some explicative examples. A theoretical proposal of a psychrometric transformation, to be performed in a HVAC system equipped with a MOF-Assisted Dehumidifier (MAD), is presented. This transformation is compared with a traditional one (cooling and dehumidification operated by a cooling coil with low temperatures of the coolant). The preliminary numerical simulations, conducted on a reference case study in Florence, Italy, show an estimated energy saving of 30–50%, leading us to consider the use of this technology as a very competitive one in the air-conditioning sector. [ABSTRACT FROM AUTHOR]

The metalloligand approach was used to obtain a novel CuII/ZnII heterobimetallic coordination polymer (CP) 1, based on the carefully designed bispidine ligand L4. CP 1, characterized by single crystal (SC‐) and powder X‐ray diffraction methods (P‐XRD), is constituted by repeating large 32‐membered macrocycles forming ribbon‐like linear arrays and it features a CuII‐coordination site occupied by a markedly labile MeCN. We also describe the synthesis and characterization of intermediate metalloligands (with CuII, FeIII, MnII, and PdII, the latter three obtained as SCs and characterized accordingly) and provide a view of potential intermediate species along the route from metalloligands to heterometallic CPs. [ABSTRACT FROM AUTHOR]

One‐dimensional (1D) coordination polymers (CPs) featuring three different topologies, comprising zig‐zag, ribbon‐like and poly‐[n]‐catenane structures, were obtained by reaction of Hg(II) ions with a novel bispidine ligand L3, and structurally characterized by SC‐ and P‐XRD methods. The CPs obtained in the form of microcrystalline powders were tested for their ability to undergo solvent adsorption and exchange by P‐XRD and 1H NMR spectroscopy. The extent of their dynamic behavior was then correlated to their structural features, highlighting the role of interchain interactions established among their constituting linear arrays. Zig‐zag CPs proved to be resilient to external chemical stimuli, while they differently respond to thermal treatments, depending on the solvent originally included within the CP. In the case of polycatenated structures, we observed transformations where the original topology was maintained upon guest exchange, but also cases where it changed to zig‐zag, even under solid/vapor conditions (i. e. no complete dissolution of the CP). Given the presence of linear interconnected 1D channels, 3 ⋅ ClBz‐polycatenanePwd is also able to trap volatile guests such as n‐hexane when exposed to its vapors. [ABSTRACT FROM AUTHOR]

The objective of this paper is to devise a general framework to allow a human operator to physically interact with an object manipulated by a multi-manipulator system in a distributed setting. A two layer solution is devised. In detail, at the top layer an arbitrary virtual dynamics is considered for the object with the virtual input chosen as the solution of an optimal Linear Quadratic Tracking (LQT) problem. In this formulation, both the human and robots’ intentions are taken into account, being the former online estimated by Recursive Least Squares (RLS) technique. The output of this layer is a desired trajectory of the object which is the input of the bottom layer and from which desired trajectories for the robot end effectors are computed based on the closed-chain constraints. Each robot, then, implements a time-varying gain adaptive control law so as to take into account model uncertainty and internal wrenches that inevitably raise due to synchronization errors and dynamic and kinematic uncertainties. Remarkably, the overall solution is devised in a distributed setting by resorting to a leader-follower approach and distributed observers. Simulations with three 6-DOFs serial chain manipulators mounted on mobile platforms corroborate the theoretical findings. [ABSTRACT FROM AUTHOR]

Here we report novel bispidine-based coordination polymers (CPs) 2·TCM, 3·TCM, 3·NB, 5·TCM and 5·TCM·NB, of compostition [Mn(Cl)2(L2)2·(TCM)2], [Mn(Cl)2(L3)2·(TCM)5], [Mn(Cl)2(L3)2·(NB)8], [Mn(Cl)2(L5)2·(TCM)4], [Mn(Cl)2(L5)2·(TCM)2·(NB)2], respectively (NB = nitrobenzene; TCM = chloroform). They were obtained starting from novel bispidine ligands L2 (dimethyl 7-isopropyl-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate), L3 (dimethyl 7-(cyclohexylmethyl)-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate) and L5 (dimethyl 7-(4-(dimethylamino)benzyl)-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate), The novel CPs were characterized by single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD) and thermal analyses (TGA). We describe their structural and dynamic properties in terms of solvent exchange and adsorption processes, and we outline the general trends observed on the basis of a total of 16 X-ray structures (4 new) and 21 microcrystalline powder phases (10 new), which have been obtained so far for CPs by coordination of ligands L1–L5, having different substitution at the N7 position. This large set of CPs comprises monosolvated, bisolvated and desolvated species, and it shows a good demonstration of how small differences in the functionalization of the organic ligand can have a strong impact on the resulting structural and dynamic properties of this class of 1D CPs. [ABSTRACT FROM AUTHOR]

Pyridine-based bispidine ligands L1–L7, which differ in the substituent at the N7 position of the bispidine scaffold, have been studied by single crystal X-ray diffraction and density functional theory (DFT) calculations, also including solid-state algorithms. Qualitative description of the packing interactions and quantitative data on the stability of each ligand in the solid-state have been employed to draw reasonable predictions on the ligand potential for the formation of linear 1D coordination polymers (CPs) with Mn(II)Cl2 and on their resulting dynamic properties, in terms of adsorption and solvent exchange capabilities. The basic assumption lies in the fact that volume and polarizability of the ligands would similarly affect packing energies in both molecular solids and CP materials. The results here obtained confirm the data previously reported on CPs (those made from L4 are less dynamic than the ones with L1), but they also allow the prediction that CPs made with L2 and L5 should be more dynamic than expected, while CPs with L6 and L7 should not form altogether. This latter prediction was derived from the analysis of the steric and electronic factors of the ligand substituents on the N7 position and it is further substantiated by the obtainment of a 2 : 1 molecular complex, and not a CP, by crystallization of L6 with MnCl2. [ABSTRACT FROM AUTHOR]

The first ab initio synchrotron powder X-ray diffraction (XRD) data structure solution, employing real-space global optimization strategies followed by Rietveld refinement, was obtained for a bispidine based one-dimensional ribbon-like coordination polymer (CP) 1. The structure solution of 1, a non-dynamic phase containing no solvent molecules, is crucial to obtain a more comprehensive view of the dynamic behaviour of a new family of 1D CPs, in terms of solvent adsorption and exchange processes by direct comparison among the structures, solvent–ribbon and inter-ribbon interactions of the CP materials. This work also reports novel bisolvated phases, 1·TCM·oNT , 1·TCM·pCT and 1·TCM·NB, in the form of single crystals and microcrystalline powders and shows that 1 can be thermally activated to regain dynamic selective adsorption features. [ABSTRACT FROM AUTHOR]

A multi‐component Povarov reaction was used for the preparation of [4], [5] and [6]aza‐ and azaoxahetero helical‐shaped compounds. The oxidation of the tetrahydroquinolinic primary Povarov adducts to the aromatic quinolines is mandatory to achieve a helical‐shaped structure and can be carried out in a one‐pot fashion with DDQ. Resolution of [5] and [6]heterohelicenes was successfully performed by chiral HPLC. TOC Text. [4], [5] and [6]aza‐ and azaoxahelical shaped compounds are prepared in a multi‐component process with a Povarov reaction as key step. DDQ oxidation of the primary tetrahydroquinolinic Povarov adducts, mandatory to achieve helical‐shaped quinolines, is run in a practical one‐pot procedure. Chiral HPLC allowed the resolution of [5] and [6]heterohelicene derivatives. [ABSTRACT FROM AUTHOR]

Ligands L1 and L2 have been designed, synthesized, and used to build for the first time bispidine‐based coordination polymers (CPs) in combination with MnII. The novel CPs have been structurally characterized by single‐crystal (SC) and powder X‐ray diffraction (P‐XRD) techniques, showing that they are composed of 1D ribbon‐like chains that adopt various arrangements depending on the trapped solvent species. These materials show highly dynamic behavior as they undergo heterogeneous solid/liquid and solid/vapor multiple solvent exchange processes, comprising crystalline–amorphous–crystalline, selective adsorption and SC‐to‐SC transformations, where major structural reorganization of the 1D ribbons are observed. By tuning inter‐ribbon interactions through expansion of the ligand's accessible surface, the dynamic behavior can be effectively modulated. The first bispidine‐based 1D coordination polymers reported here show unique dynamic behavior, including crystalline‐to‐amorphous‐to crystalline, selective adsorption, and single crystal to single crystal solvent exchange transformations. System tunability can be easily achieved by structural modification of the bispidine ligand. [ABSTRACT FROM AUTHOR]

The control of airborne contaminants is of great interest in improving air quality, which has deteriorated more and more in recent years due to strong industrial growth. In the last decades, cellulose has been largely proposed as suitable feedstock to build up eco-friendly materials for a wide range of applications. Herein, the issue regarding the use of cellulose to develop air-filtering systems is addressed. The review covers different cellulose-based solutions, ranging from aerogels and foams to membranes and films, and to composites, considering either particulate filtration (PM10, PM2.5, and PM0.3) or gas and water permeation. The proposed solutions were evaluated on the bases of their quality factor (QF), whose high value (at least of 0.01 Pa−1 referred to commercial HEPA (high-efficiency particulate air) filters) guarantees the best compromise between high filtration efficiency (>99%) and low pressure drop (<1 kPa/g). To face this aspect, we first analyzed the different morphological aspects which can improve the final filtration performance, outlining the importance on using nanofibers not only to increase surface area and to modulate porosity in final solutions, but also as reinforcement of filters made of different materials. Besides the description of technological approaches to improve the mechanical filtration, selected examples show the importance of the chemical interaction, promoted by the introduction of active functional groups on cellulose (nano)fibers backbone, to improve filtration efficiency without reducing filter porosity. [ABSTRACT FROM AUTHOR]